JP2003100217A - Electrode material and plasma display using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide electrode materials which are capable of realizing low power consumption and prolonging the service life by reducing discharge start voltages, and also provide a plasma display using it. SOLUTION: In this plasma display panel, a first substrate, on which a plurality of pairs formed of pair of a first electrode and a second electrode disposed in strip form are formed and the pairs with one pair of electrodes are coated with dielectric, and a second substrate, on which a third electrodes are disposed in strip form, are arranged facing each other by disposing barrier ribs between the substrates. Here, the dielectric layer is shown by a composition formula AlNX, where X is at least one kind chosen from among the group of Si, Sn, Pb, Be, Mg, Ca, O, and S.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma display panel used for a display device or the like, and more particularly to a panel structure for improving discharge characteristics such as discharge voltage and spatter resistance.

[0002]

2. Description of the Related Art Conventional plasma display panels are
The structure shown in FIG. 1 is generally used.

This plasma display panel comprises a front panel PA1 and a rear panel PA2. The front panel PA1 includes a scanning electrode 12a on the front glass substrate 11,
The sustain electrodes 12b are alternately formed in stripes, and are further covered with the dielectric glass layer 13 and the protective layer 14.

The rear panel PA2 is a rear glass substrate 16
An address electrode 17 is formed in a stripe shape on the upper side, an electrode protection layer 18 is formed so as to cover the address electrode 17, and a partition wall 19 is formed in a stripe shape on the electrode protection layer 18 so as to sandwich the address electrode 17. Phosphor layer 2 between partition walls 19
0 is provided and formed. Then, the front panel PA1 and the rear panel PA2 are bonded together, and a discharge gas is enclosed in the space 30 partitioned by the partition wall 19 to form a discharge space. The color of the phosphor layer is usually three phosphor layers of red, green, and blue arranged in order for color display.

In the discharge space 30, for example, a discharge gas formed by mixing neon and xenon is usually 0.67.
It is sealed at a pressure of about 10 ⁵ Pa.

Next, a driving method of the plasma display panel will be described.

FIG. 2 is a block diagram showing a configuration of a driving circuit of the plasma display panel.

The drive circuit comprises an address electrode drive section 22.
0, the scan electrode driver 230, and the sustain electrode driver 240
It consists of and.

An address electrode driver 220 is connected to the address electrodes 17 of the plasma display panel, a scan electrode driver 230 is connected to the scan electrodes 12a, and a sustain electrode driver 240 is connected to the sustain electrodes 12b.

Generally, in an AC type plasma display panel, one frame image is displayed in a plurality of subfields (S.
F.) is used to express gradation. Then, in this method, in order to control the discharge of gas in the cell, 1S. F. Is further divided into four periods. The four periods will be described with reference to FIG. FIG. 3 is a drive waveform during 1SF.

In FIG. 3, the setup period 250
Then, wall charges are uniformly accumulated in all cells in the PDP in order to facilitate discharge. In the address period 260, the writing discharge of the cell to be turned on is performed. In the sustain period 270, the cell written in the address period 260 is lit and the lit state is maintained. Erase period 280
Then, the wall charge is erased to stop the lighting of the cell.

In the setup period 250, the scan electrode 12
A higher voltage than that of the address electrode 17 and the sustain electrode 12b is applied to a to discharge the gas in the cell. Since the charges generated thereby are accumulated on the wall surface of the cell so as to cancel the potential difference between the address electrode 17, the scan electrode 12a and the sustain electrode 12b, negative charges are generated as wall charges on the surface of the protective film near the scan electrode 12a. In addition, positive charges are accumulated as wall charges on the surface of the phosphor layer near the address electrodes and the surface of the protective film near the sustain electrodes. Due to this wall charge, a wall potential having a predetermined value is generated between the scan electrode and the address electrode and between the scan electrode and the sustain electrode.

In the address period 260, when the cell is turned on, a voltage lower than that applied to the address electrode 17 and the sustain electrode 12b is applied to the scan electrode 12a, that is, between the scan electrode and the address electrode in the same direction as the wall potential. A voltage is applied to the scan electrodes and a voltage is applied between the scan electrodes and the sustain electrodes in the same direction as the wall potential to generate the write discharge. As a result, negative charges are accumulated on the surface of the phosphor layer and the protective layer, and positive charges are accumulated as wall charges on the surface of the protective layer near the scanning side electrode. As a result, a wall potential having a predetermined value is generated between the sustain and scan electrodes.

In the sustain period 270, the scan electrode 12a is formed.
By applying a voltage higher than that of the sustain electrode 12b, that is, by applying a voltage between the sustain electrode and the scan electrode in the same direction as the wall potential, the sustain discharge is generated.
As a result, cell lighting can be started. Then, by applying a pulse so that the polarities of the sustain electrodes and the scan electrodes are alternately switched, it is possible to intermittently emit pulsed light.

In the erase period 280, by applying a narrow erase pulse to the sustain electrode 12b, an incomplete discharge occurs and wall charges disappear, so that erase is performed.

[0016]

By the way, as described above, conventionally, the dielectric protective layer 14 of the plasma display panel serves to protect the original dielectric, and at the same time, the AC type plasma display as described above. Since it is a part of the panel that is directly exposed to the discharge space, its function as an actual electrode is also important. At present, magnesium oxide (MgO) is used for this dielectric protective layer.
This is because it was considered to be better than the other materials in two points of the sputter resistance electron emission characteristics, which are the necessary conditions for the above-mentioned dielectric protective layer.

On the other hand, this MgO also has a characteristic that it has a very strong hygroscopic property. Therefore, a large amount of gas such as H ₂ O and CO ₂ will be adsorbed on the MgO surface depending on the storage condition after the MgO film formation. These gases are not completely removed from the MgO surface and the discharge space in the exhaust step after the panel is formed, but remain taken in as an impurity gas in the discharge space. It is considered that this is due to the adsorption state of gas to MgO and the conductance in a narrow space due to the bonded panel.

However, the presence of the impurity gas in these panels greatly affects the discharge state. For example, H ₂ O
In the case of, these react with MgO and change to Mg (OH) ₂ , and in the case of CO _2, they change to MgCO ₃ and their presence on the surface lowers the electron emission ability as a protective film, thus starting discharge. The voltage will rise significantly.

Further, when these impurity gases are discharged into the discharge gas due to the sputtering action at the time of lighting, the deterioration of the phosphor is promoted, which also becomes a factor to shorten the life of the product. .

The present invention has been made in view of the above problems, and provides a dielectric protective layer having sputter resistance and electron emission characteristics equal to or higher than those of MgO and hardly affected by impurity gas. The purpose of the present invention is to provide a provided plasma display panel and a manufacturing method thereof.

[0021]

[Means for Solving the Problems] In this way, P
In addition to the above-mentioned conditions, the characteristics required for the DP protective film are that the amount of adsorbed gas is small.

Therefore, as a result of various studies, the inventors have found that a film having a basic composition of aluminum nitride (AlN) is very effective as the dielectric protection layer.
Compared with MgO, AlN has a smaller electron affinity, bandgap, etc., and is very excellent in electron emission capability.

AlN has almost no hygroscopicity, and its sputter resistance is superior to that of MgO.

Further, it was found that by mixing a certain amount of elements other than Al and N into this AlN, the electron emission characteristics and the sputter resistance are further improved.

Further, magnesium oxide (MgO) is used as a basic composition for the dielectric protective layer, and magnesium oxide (MgO) is used.
It was found that by mixing a certain amount of elements other than Mg and O into (O), the electron emission characteristics and the sputtering resistance are further improved.

From the above viewpoints, the inventors have conceived the present invention.

That is, according to the present invention, a plurality of electrode pairs of a first electrode and a second electrode arranged in stripes are arranged in parallel,
Further, a first substrate in which the plurality of pairs of electrodes are covered with a dielectric layer and a second substrate in which the third electrodes are arranged in stripes
Substrate is a plasma display panel arranged in a state of being opposed to each other with a partition interposed, wherein the dielectric layer is represented by AlNX, and X is Si, Ge, Sn, Pb, Be,
It is characterized by being coated with at least one selected from Mg, Ca, O and S.

[0028] Furthermore, where the AlNX a composition _{formula, (Al 1-ab M a} D b) (N 1-c A c) (M is, Si, Ge, Sn, Pb
At least one selected from Be, Mg, and Ca, A is at least one selected from O and S), and 0 ≦≦ a ≦≦ 0.5, 0 ≤b≤0.5, 0≤a + b
It is desirable that the range is ≦ 0.5, 0 ≦ c ≦ 0.5, and 0 <a + b + c ≦ 1.

Further, at least one element selected from the element M (M is an element selected from Si, Ge, Sn, and Pb) or the element A (A is an element selected from O and S) is included, and n It is desirable that the structure is doped into a mold, and it contains at least one element selected from the element D (D is an element selected from Be, Mg, and Ca), and is P-type. It is desirable to be characterized as being doped.

Further, the element M (M is an element selected from Si, Ge, Sn and Pb) or the element A (A is an element selected from O and S)
At least one element selected from the elements and element D (D is B
It is preferable that at least one element selected from e, Mg, and Ca) is simultaneously contained.

Further, in the discharge electrode material having at least AlN as a mother structure, at least a part of the atomic position of Al is S
At least 1 selected from i, Ge, Sn, Pb, Be, Mg, Ca
It is preferable that at least one part of the element N is replaced with at least one kind of element selected from O and S.

The composition formula (Al _1-ab M _a D _b ) _1- δ (N
_1-c A _c ) δ (M is at least one selected from Si, Ge, Sn, and Pb, and D is at least one selected from Be, Mg, and Ca.
Species, A is at least one selected from O and S),
It is desirable to be characterized in that 0.3 <δ <0.5.

Further, the AlNX or formed on a substrate _{(Al 1-ab M a D} b) (N 1-c A c) or _{(Al 1-ab M a D} b) 1-
The crystal orientation plane of δ (N _1-c A _c ) δ is at least (002)
It is desirable that the surface is preferentially oriented.

As an invention which obtains the same effect, the dielectric layer is represented by MgOX, and the X is Al, Ga, Li, F, C.
It is desirable that at least one selected from l, N, and P is characterized.

Furthermore, here, the above-mentioned MgOX is a composition formula, (Mg _1-ab M _a D _b ) (O _1-cd A _c Z _d ) (M is Al, Ga,
At least one selected from Si, Ge, Sn, D for Li, A for
At least one selected from F and Cl, Z is at least one selected from N and P), and 0 ≦ a ≦ 0.5, 0 ≦ b ≦ 0.
5, 0 ≦ a + b ≦ 0.5, 0 ≦ c ≦ 0.5, 0 ≦ d ≦ 0.5, 0 <a + b + c + d
It is desirable that the range is ≦ 1.

At least one element selected from the element M (M is an element selected from Al, Ga, Si, Ge, Sn) or the element A (A is an element selected from F and Cl) At least one selected from the elements D (D is Li) or Z (Z is an element selected from N and P). Containing elements of
It is desirable that it is p-type doped.

At least one element selected from the element M (M is an element selected from Al, Ga, Si, Ge and Sn) or the element A (A is an element selected from F and Cl) And element D
It is desirable that at least one element selected from (D is Li) or Z (Z is an element selected from N and P) is simultaneously contained.

Further, in a discharge electrode material having at least MgO as a mother structure, at least a part of the atomic position of Mg is A
It is substituted with at least one element selected from l, Ga and Li, and at least part of the element O is F, Cl,
It is desirable that it is substituted with at least one element selected from N and P.

Further, the composition _{formula, (Mg 1-ab M a} D b) 1- δ (O
_1-cd A _c Z _d ) δ (M is at least one selected from Al, Ga, Si, Ge, and Sn, D is Li, A is at least one selected from F and Cl, and Z is N. , P at least one), and 0.3 <δ <0.5 is preferable.

Further, the above-mentioned MgOX formed on the substrate
Or (Mg_1-abM_aD_b) (O_1-cdA_cZ _d) Or (Mg_1-ab
M_aD_b)_1-δ (O_1-cdA_cZ_d) The crystal orientation plane of δ is (11
Either 1) or (200) or (220)
It is desirable to be characterized by taking a preferential orientation of planes.

Further, the AlNX or _{(Al 1-ab M a D} b)
(N _1-c A _c ) or (Al _1-ab M _a D _b ) _1- δ (N _1-c A _c ) δ or MgOX or (Mg _1-ab M _a D _b ) (O _1-cd A _c Z _d )
Or _{(Mg 1-ab M a D} b) 1- δ (O 1-cd A c Z d) δ is formed on the substrate, and a feature that it has a composition modulation structure in a direction perpendicular to the substrate surface It is desirable to do.

Further, the above-mentioned AlNX or (Al _1-ab M _a D _b )
(N _1-c A _c ) or (Al _1-ab M _a D _b ) _1- δ (N _1-c A _c ) δ or MgOX or (Mg _1-ab M _a D _b ) (O _1-cd A _c Z _d )
Or _{(Mg 1-ab M a D} b) 1- δ (O 1-cd A c Z d) δ is formed on the substrate, and desirably characterized by having a columnar structure, or even columnar The width of the crystal having a structure is preferably 50 nm to 3000 nm, and further, the columnar structure is in the range of 30 <α <90 degrees when the inclination with respect to the substrate surface is α. Is desirable.

Further, the above-mentioned AlNX or (Al _1-ab M _a D _b )
(N _1-c A _c ) or (Al _1-ab M _a D _b ) _1- δ (N _1-c A _c ) δ or MgOX or (Mg _1-ab M _a D _b ) (O _1-cd A _c Z _d )
Or _{(Mg 1-ab M a D} b) 1- δ (O 1-cd A c Z d) δ is formed on the substrate, and characterized by having a lattice strain of 2% at least 0.1% or more It is desirable to do.

Further, the above-mentioned AlNX or (Al _1-ab M _a D _b )
(N _1-c A _c ) or (Al _1-ab M _a D _b ) _1- δ (N _1-c A _c ) δ or MgOX or (Mg _1-ab M _a D _b ) (O _1-cd A _c Z _d )
Or _{(Mg 1-ab M a D} b) 1- δ thickness of _{(O 1-cd A c Z} d) δ it is desirable, characterized in that at 1000nm less than 0.05 nm.

As a result, as compared with the conventional MgO, a very good film can be obtained as the dielectric protective layer in terms of electron emission characteristics, sputtering resistance, and reduction of the amount of adsorbed impurity gas.

[0046]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an AC type plasma display panel according to an embodiment of the present invention will be specifically described with reference to the drawings.

(Embodiment) FIG. 1 shows a conventional AC surface discharge type plasma display panel 1 (hereinafter, simply referred to as PDP1).
Say. 3) is a partial perspective view of FIG.

As described above, the PDP 1 discharges the discharge space 30 by applying a pulsed voltage to each electrode.
It is an AC surface discharge type PDP that allows the visible light of each color that is generated inside and is generated on the side of the rear panel PA2 with the discharge to pass from the main surface of the front panel PA1.

Front panel PA1 covers front surface 11a on front glass substrate 11 in which a plurality of pairs of scan electrodes 12a and sustain electrodes 12b are arranged in stripes (a pair is shown for convenience in the figure). The dielectric glass layer 13 is formed, and the protective layer 14 is further formed so as to cover the dielectric glass layer 13.

The rear panel PA2 protects the address electrodes 17 on the rear glass substrate 16 arranged in stripes so that the address electrodes 17 are orthogonal to the scan electrodes 12a and the sustain electrodes 12b. In addition, an electrode protective layer 18 having a function of reflecting visible light to the front panel side is formed, and a partition wall is formed on the electrode protective layer 18 so as to extend in the same direction as the address electrode 17 and sandwich the address electrode 17. 19 are provided upright, and a phosphor layer 20 is further disposed between the partition walls 19.

The PDP having the above structure is driven based on the drive waveform shown in FIG. 3 using the drive circuit shown in FIG. The address electrodes 17 are connected to the address driver 220, the scan electrodes 12a are connected to the scan electrode driver 230, and the sustain electrodes 12b are connected to the sustain electrode driver 240.

In the present invention, the composition of the protective film 14 is different.

Each embodiment will be described in detail below.

Next, a specific example of the present invention will be described. The discharge starting point pressure and the sputtering resistance were used for the evaluation of each composition as a protective layer. As the discharge start voltage, the voltage value required for in-plane discharge in the scan electrode 12a and the sustain electrode 12b of the PDP 1 is set to Mg.
Compared with O, the case where the voltage value is equal to or less than MgO is indicated by ◯, and the other cases are indicated by x. Here, when the discharge starting voltage was MgO of 100, the discharge starting voltage of the protective layer of each composition was equal to 120. Further, the sputter resistance shows the value of the film thickness reduction rate 1000 hours after the start of discharge when the change amount of MgO is 100.

Example 1 In the example of the embodiment described below, the protective layer is represented by the composition formula AlNX, where X is Si, Ge,
This is the case where at least one selected from Sn, Pb, Be, Mg, Ca, O, and S is used. The protective layer materials within the scope of the examples of the present invention are shown in Table 1, Table 2, Table 3 and Table 4.
In addition, the amount of change in the discharge start voltage and the film thickness reduction rate is shown.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4]

[0060]

[Table 5]

[0061]

[Table 6]

[0062]

[Table 7]

According to Table 1, Table 2, Table 3 and Table 4, as compared with the conventional protective layer MgO, in the protective layer of the material within the range of the embodiment of the present invention, the film thickness reduction rate is MgO. It is about 90% compared with the above, and the improvement of the sputter resistance can be seen. On the other hand, the discharge starting voltage is equal to or less than that of the conventional MgO protective layer, and the characteristics are good.

Compositional formula, (Al _1-ab M _a D _b ) (N _1-c A _c ) (M
Is at least one selected from Si, Ge, Sn, and Pb, D
Is at least one selected from Be, Mg and Ca, A is O and S
From at least one selected from Table 1, Table 2, Table 3 and Table 4 and M is 0.03 to 0.11 (M is at least one selected from Si, Ge, Sn and Pb). When it is in the range, the discharge start voltage and spatter resistance are particularly good, and when it is in the range of 0.30 to 0.38, the discharge start voltage and spatter resistance are particularly good. Similar results were obtained in the range of 0.00 to 0.50 for compositions other than those in Table 1, Table 2, Table 3, and Table 4, and the discharge starting voltage and spatter resistance were particularly good. However, when it is 0.52 or more, no improvement in characteristics is observed.

From Table 1, Table 2, Table 3 and Table 4, D is 0 (D is at least one selected from Be, Mg and Ca).
When it is in the range of 03 to 0.11, it is particularly good, and when it is in the range of 0.30 to 0.41, the discharge starting voltage and spatter resistance are particularly good. Similar results were obtained in the range of 0.00 to 0.50 for compositions other than those in Table 1, Table 2, Table 3, and Table 4, and the discharge starting voltage and spatter resistance were particularly good. However, when it is 0.61 or more, no improvement in characteristics is observed.

From Table 1, Table 2, Table 3 and Table 4, M (M
Is at least one selected from Si, Ge, Sn, and Pb) and D
When the total amount of (D is at least one selected from Be, Mg and Ca) is in the range of 0.37 to 0.45, the discharge starting voltage and the spatter resistance are particularly good. Even in compositions other than Table 1, Table 2, Table 3, and Table 4, 0.00 to
Similar results are obtained in the range of 0.50, and the discharge starting voltage and the spatter resistance are particularly good. But 0.5
When it is 5 or more, no improvement in characteristics is observed.

From Table 1, Table 2, Table 3, and Table 4, A is 0.03 (A is at least one selected from O and S).
When it is in the range of 0.10, the discharge starting voltage and the sputtering resistance are particularly good. Similar results were obtained in the range of 0.00 to 0.50 for compositions other than those in Table 1, Table 2, Table 3, and Table 4, and the discharge starting voltage and spatter resistance were particularly good. However, when it is 0.54 or more, no improvement in characteristics is observed.

From Table 1, Table 2, Table 3 and Table 4, M (M
Is at least one selected from Si, Ge, Sn, and Pb) and D
(D is at least one selected from Be, Mg and Ca) and A
When the total amount of (A is at least one selected from O and S) combined is in the range of 0.41 to 0.52, the discharge starting voltage and the sputtering resistance are particularly good. The composition other than Table 1, Table 2, Table 3 and Table 4 is 0.00 to 1.0.
In the range of 0, similar results are obtained, and the discharge starting voltage and spatter resistance are particularly good. However, when it is 1.00 or more, no improvement in characteristics is observed.

Therefore, the composition formula, (Al _1-ab M _a D _b ) (N
_1-c A _c ) (M is at least one selected from Si, Ge, Sn, and Pb, D is at least one selected from Be, Mg, and Ca, A
Is at least one selected from O and S), and 0 ≦ a ≦ 0.5, 0
It can be seen that the discharge start voltage and the spatter resistance are particularly good in the range of ≦ b ≦ 0.5, 0 ≦ a + b ≦ 0.5, 0 ≦ c ≦ 0.5, 0 <a + b + c ≦ 1. .

In the examples of the present invention, the above sample was prepared by a sputtering method using an alloy target and a powder target. However, the method is not limited to this method, and a sputtering method using a target having the above composition or the like. In addition, the same effect can be obtained by the electron beam evaporation method using the evaporation source having the above composition.

(Example 2) In the following example, the protective layer is the element M (M is an element selected from Si, Ge, Sn, and Pb) or A (A is an element selected from O and S). This is a case where the film contains at least one element selected from the above and is doped to the n-type. From the temperature characteristics of the resistance value of each composition, the resistance value is 10 ⁶ to 10 ¹² Ωcm and the semiconductor-like behavior is exhibited. Therefore, it is judged that the material is an n-type doped material, judging from the load number of the element used. did. Table 2 shows protective layer materials within the scope of the examples of the present invention. In addition, the amount of change in the discharge start voltage and the film thickness reduction rate is shown.

According to Table 2, as in Example 1, the protective layer made of the material within the range of Examples of the present invention has a particularly good discharge starting voltage, as compared with the conventional protective layer composition of MgO. . On the other hand, the sputtering resistance is also better than that of the conventional MgO protective layer.

In the examples of the present invention, the above-mentioned sample was prepared by a sputtering method using an alloy target and a powder target. However, the present invention is not limited to this method, and a sputtering method using a target having the above composition, or the like. In addition, the same effect can be obtained by the electron beam evaporation method using the evaporation source having the above composition.

(Example 3) In the following example, the protective layer contains at least one element selected from the element D (D is an element selected from Be, Mg and Ca) and is a P-type dopant. -For pinged cases. From the temperature characteristics of the resistance value of each composition, since the resistance value is 10 ⁶ to 10 ¹² Ωcm and the semiconductor-like behavior is shown, judging from the load number of the element used,
It is assumed to be a p-type doped material. Table 3 shows protective layer materials within the scope of the examples of the present invention. In addition, the amount of change in the discharge start voltage and the film thickness reduction rate is shown.

According to Table 3, as in Examples 1 and 2, the discharge starting voltage was particularly good in the protective layer made of the material within the range of Examples of the present invention, as compared with the conventional protective layer composition of MgO. I know there is. On the other hand, the sputtering resistance is also better than that of the conventional MgO protective layer.

In the examples of the present invention, the above sample was prepared by a sputtering method using an alloy target and a powder target. However, the method is not limited to this method, and a sputtering method using a target having the above composition or the like. In addition, the same effect can be obtained by the electron beam evaporation method using the evaporation source having the above composition.

(Embodiment 4) In the embodiment described below, the protective layer has an element M (M is an element selected from Si, Ge, Sn and Pb) or an element A (A is an element selected from O and S). And at least one element selected from the elements D (D is an element selected from Be, Mg, and Ca) at the same time, and the composition formula (Al _1-ab M _a D _b ) _1- δ (N _1-c A _c ) δ
(M is at least one selected from Si, Ge, Sn and Pb, D
Is at least one selected from Be, Mg and Ca, A is O and S
At least one selected from the above, and the case of 0.3 <δ <0.5.

According to Table 4, as in Example 1, Example 2 and Example 3, the discharge start voltage was higher in the protective layer made of the material within the range of Example of the present invention than in the conventional protective layer composition of MgO. It can be seen that is particularly good. On the other hand, the sputtering resistance is also better than that of the conventional MgO protective layer.

In the examples of the present invention, the above sample was prepared by a sputtering method using an alloy target and a powder target. However, the present invention is not limited to this method, and a sputtering method using a target having the above composition or the like. In addition, the same effect can be obtained by the electron beam evaporation method using the evaporation source having the above composition.

(Embodiment 5) In the embodiment of the embodiment described below, the protective layer is represented by the composition formula MgOX, where X is Al, Ga, L.
The case is at least one selected from i, F, Cl, N, and P. Tables 5, 6, 6, and 8 show protective layer materials within the scope of the examples of the present invention. In addition, the amount of change in the discharge start voltage and the film thickness reduction rate is shown.

[0081]

[Table 8]

[0082]

[Table 9]

[0083]

[Table 10]

[0084]

[Table 11]

[0085]

[Table 12]

[0086]

[Table 13]

[0087]

[Table 14]

According to Table 5, Table 6, Table 7, and Table 8, as compared with the conventional protective layer of MgO, the protective layer of the material within the range of the embodiment of the present invention showed a film thickness reduction rate of about It is 90%, and improvement in spatter resistance can be seen. On the other hand, the discharge start voltage is also equal to or lower than that of the conventional MgO protective layer, which is good.

Compositional formula, compositional formula (Mg _1-ab M _a D _b ) (O _1-cd
A _c Z _d ) (M is at least one selected from Al, Ga, Si, Ge, and Sn, D is Li, and A is at least 1 selected from F and Cl.
And Z is at least one selected from N and P) and M is at least one selected from Table 5, Table 6, Table 7 and Table 8 (M is at least one selected from Al, Ga, Si, Ge and Sn). ) When it is in the range of 0.02 to 0.12, the discharge start voltage and spatter resistance are particularly good, and when it is in the range of 0.29 to 0.35, the discharge start voltage and spatter resistance are particularly good. It is good. Even in compositions other than Table 5, Table 6, Table 7, and Table 8, 0.00 to
Similar results are obtained in the range of 0.50, and the discharge starting voltage and the spatter resistance are particularly good. But 0.5
When it is 1 or more, no improvement in characteristics is observed.

Further, from Table 5, Table 6, Table 7 and Table 8, when D is in the range of 0.02 to 0.09 (D is Li), the discharge starting voltage and the spatter resistance are particularly good, When it is in the range of 0.30 to 0.37, the discharge starting voltage and the spatter resistance are particularly good. Similar results were obtained in the range of 0.00 to 0.50 for compositions other than those in Table 5, Table 6, Table 7, and Table 8, and the discharge starting voltage and spatter resistance were particularly good. However, when it is 0.61 or more, no improvement in characteristics is observed.

From Table 5, Table 6, Table 7 and Table 8, M (M
Is at least one selected from Al, Ga, Si, Ge, and Sn)
And D (D is Li) combined is 0.02-0.09
The discharge starting voltage and the sputter resistance are particularly good in the range of 1, and the discharge start voltage and the sputter resistance are particularly good in the range of 0.36 to 0.45. Even in the compositions other than Table 5, Table 6, Table 7 and Table 8, it is 0.
In the range of 00 to 0.50, similar results are obtained, and the discharge starting voltage and the sputter resistance are particularly good. But,
When it is 0.61 or more, no improvement in characteristics is observed.

From Table 5, Table 6, Table 7 and Table 8, A is 0.01 to (A is at least one selected from F and Cl).
When it is in the range of 0.07, the discharge starting voltage and the sputtering resistance are particularly good. Similar results were obtained in the range of 0.00 to 0.50 for compositions other than those in Table 5, Table 6, Table 7, and Table 8, and the discharge starting voltage and spatter resistance were particularly good. However, when it is 0.51 or more, no improvement in characteristics is observed.

From Table 5, Table 6, Table 7, and Table 8, Z is 0.01 to (Z is at least one selected from N and P).
When it is in the range of 0.02, the discharge starting voltage and the sputtering resistance are particularly good. Similar results were obtained in the range of 0.00 to 0.50 for compositions other than those in Table 5, Table 6, Table 7, and Table 8, and the discharge starting voltage and spatter resistance were particularly good. However, when it is 0.51 or more, no improvement in characteristics is observed.

From Table 5, Table 6, Table 7, and Table 8, M (M
Is at least one selected from Al, Ga, Si, Ge, and Sn)
And D (D is Li), A (A is at least 1 selected from F and Cl) and Z (Z is at least one selected from N and P) and the total amount is 0.39 to 0. When it is in the range of 48, the discharge starting voltage and the sputtering resistance are particularly good. Even in compositions other than Table 5, Table 6, Table 7, and Table 8, 0.00 to
Similar results are obtained in the range of 1.00, and the discharge starting voltage and the spatter resistance are particularly good. But 1.0
When it is 0 or more, no improvement in characteristics is observed.

[0095] Thus formula _{(Mg 1-ab M a D} b) (O 1-cd A c
_Zd ) (M is at least one selected from Al, Ga, Si, Ge, and Sn, D is Li, and A is at least one selected from F and Cl.
And Z is at least one selected from N and P), and 0 ≦ a ≦
≦ 0.5, 0 ≦ b ≦ 0.5, 0 ≦ a + b ≦ 0.5, 0 ≦ c ≦ 0.5, 0 ≦ d ≦
It can be seen that in the range of 0.5 and 0 <a + b + c + d ≦ 1, the discharge starting voltage and the spatter resistance are particularly good.

In the examples of the present invention, the above sample was prepared by a sputtering method using an alloy target and a powder target. However, the present invention is not limited to this method, and a sputtering method using a target having the above composition or the like. In addition, the same effect can be obtained by the electron beam evaporation method using the evaporation source having the above composition.

(Embodiment 6) In the embodiment described below, the protective layer is the element M (M is an element selected from Al, Ga, Si, Ge and Sn).
Alternatively, it is a case in which at least one element selected from the element A (A is an element selected from F and Cl) is contained and the element is doped to the n-type. From the temperature characteristics of the resistance value of each composition, since the resistance value is 10 ⁶ to 10 ¹² Ωcm and the semiconductor-like behavior is shown, judging from the load number of the element used,
It is assumed that the material is n-type doped. Table 6 shows protective layer materials within the scope of the examples of the present invention. In addition, the amount of change in the discharge start voltage and the film thickness reduction rate is shown.

According to Table 6, as in the case of Example 5, the protective layer made of the material within the range of Examples of the present invention has a particularly good discharge starting voltage, compared to the conventional protective layer composition of MgO. . On the other hand, the sputtering resistance is also better than that of the conventional MgO protective layer.

In the examples of the present invention, the above sample was prepared by a sputtering method using an alloy target and a powder target. However, the present invention is not limited to this method, and a sputtering method using a target having the above composition or the like. In addition, the same effect can be obtained by the electron beam evaporation method using the evaporation source having the above composition.

Example 7 In the following example, the protective layer contains at least one element selected from the elements D (D is Li) or Z (Z is an element selected from N and P), This is for the case of p-type doping. From the temperature characteristics of the resistance value of each composition, since the resistance value is 10 ⁶ to 10 ¹² Ωcm and the semiconductor behavior is shown, it is judged that the material is p-type doped, judging from the load number of the element used. did. Table 7 shows protective layer materials within the scope of the examples of the present invention. In addition, the amount of change in the discharge start voltage and the film thickness reduction rate is shown.

According to Table 7, as in Examples 5 and 6, the discharge starting voltage was particularly good in the protective layer made of the material within the range of the examples of the present invention, as compared with the conventional protective layer composition of MgO. I know there is. On the other hand, the sputtering resistance is also better than that of the conventional MgO protective layer.

In the examples of the present invention, the above sample was prepared by a sputtering method using an alloy target and a powder target. However, the method is not limited to this method, and a sputtering method using a target having the above composition or the like. In addition, the same effect can be obtained by the electron beam evaporation method using the evaporation source having the above composition.

(Embodiment 8) In the embodiment described below, the protective layer is the element M (M is an element selected from Al, Ga, Si, Ge and Sn).
Alternatively, at least one element selected from the element A (A is an element selected from F and Cl) and the element D (D is Li) or Z
(Z is an element selected from N and P) at the same time contains at least one element selected from the composition formula (Mg _1-ab M
_a D _b ) _1- δ (O _{1 -cd} A _c Z _d ) δ (M is Al, Ga, Si, Ge,
At least one selected from Sn, D at least one selected from Li, A at least one selected from F and Cl, and Z at least one selected from N and P) in the range of 0.3 <δ <0.5 It is about the case.

According to Table 8, as in Example 5, Example 6 and Example 7, in the protective layer of the material within the range of the example of the present invention, the discharge starting voltage is higher than that of MgO which is the conventional protective layer composition. It can be seen that is particularly good. On the other hand, the sputtering resistance is also better than that of the conventional MgO protective layer.

In the examples of the present invention, the above sample was prepared by a sputtering method using an alloy target and a powder target. However, the present invention is not limited to this method, and a sputtering method using a target having the above composition or the like. In addition, the same effect can be obtained by the electron beam evaporation method using the evaporation source having the above composition.

(Function and Effect) As described above, by using the material containing AlN as the main component in the protective layer 14, the discharge starting voltage is lowered and the spatter resistance can be improved. It is considered that this is because AlN has a smaller electron affinity, bandgap, and the like than MgO and has a very excellent electron emission capability. Further, by mixing a certain amount of elements other than Al and N into this AlN, the electron emission characteristics can be further improved. Similarly, by using a material containing MgO as a main component, the discharge starting voltage is lowered and the spatter resistance can be improved. This is MgO,
By mixing a certain amount of elements other than Mg and O, the electron affinity, band gap, etc. are reduced,
It is considered that the factor is that the electron emission capability is excellent as compared with. Therefore, the electron emission characteristics can be further improved.

These protective layers have AlN as a mother structure and
At least a part of the atomic positions of l is Si, Ge, Sn, Pb, Be,
It is desirable that at least one element selected from Mg and Ca be substituted, and at least part of the element N be substituted by at least one element selected from O and S. desirable.

Further, it is desirable that MgO has a mother structure and at least a part of the atomic position of Mg is substituted with at least one element selected from Al, Ga and Li. It is desirable that the part is substituted with at least one element selected from F, Cl, N and P.

The substitution here means that the mother structure and the crystal structure are the same as a result of the analysis of the film structure based on XRD. By substituting, the characteristics are stable even if the crystal structure is not collapsed and the composition is changed.

The film structure of these protective layers is Al
NX or (Al _1-ab M _a D _b ) (N _1-c A _c ) or (Al _1-ab M
Regarding _a D _b ) _1- δ (N _1-c A _c ) δ, it is preferable that the crystal orientation plane is preferentially oriented to at least the (002) plane.
The electron emission characteristics and spatter resistance were good. Further, MgOx or _{(Mg 1-ab M a D} b) (O 1-cd A c Z d)
Alternatively, the crystal orientation plane of (Mg _1-ab M _a D _b ) _1- δ (O _1-cd A _c Z _d ) δ is (111) or (200) or (22
0) The electron emission characteristics and the sputter resistance were better when the orientation was preferentially oriented on either surface. Moreover, the cause of these phenomena has not been clarified yet.

Further, since these protective layers have a composition modulation structure in the direction perpendicular to the surface of the substrate on which they are formed, they exhibit further excellent electron emission characteristics and sputtering resistance. The reason is that the best characteristics can be obtained because there are films with different properties, such as a composition that is compatible with the substrate used, a composition that has the best electron emission characteristics, and a composition that has the best sputtering resistance. .

Further, the shape of the film structure of these protective layers is preferably a columnar structure. This is the discharge space 3
It is considered that the surface area where electrons are emitted toward 0 can be made large, and as a result, trigger electrons for address discharge and sustain discharge are easily emitted. The columnar structure has a crystal width of 0.005 to 3
μm, and it is desirable that the columnar portion satisfy 30 <α <90 when the inclination with respect to the film surface is α. Also, it is desirable to have a lattice strain of about 0.1% to 2%. Although the cause of this phenomenon has not been clarified yet, in the case of the protective layer film having a shape in this range, a better electron emission characteristic was exhibited.

It is desirable that the film thickness is 0.05 to 1000 nm. This is because, for example, when the thickness is less than 0.05 nm, the protective layer film is scraped off due to the sputtering effect due to discharge, and the life of the product is shortened. Because it is connected.

As a method of forming the above protective layer film, as described in the examples of the present invention, a metal target, a powder target, a sputtering method using an evaporation source, an electron beam evaporation method, or the like can be obtained. Alternatively, the same effect can be obtained by using a target vapor deposition source made with each composition ratio.

The protective layer film is formed of AlNX or (Al
_1-ab M _a D _b ) (N _1-c A _c ) or MgOX or (Mg _{1-ab
M a D b) (O 1} -cd A c Z d) and the time, the element N, A,
It is desirable that O and Z are supplied as gas during sputtering. As a result, there is an attendant effect that the formation speed at the time of mass production of the product is improved.

(PDP Manufacturing Method) Next, a PDP manufacturing method will be described.

Assembly of PDP; Preparation of Front Panel PA1: First, scan electrodes 12a and sustain electrodes 12b are formed on the front glass substrate 11 so as to be arranged alternately.

The scan electrodes 12a and the sustain electrodes 12b are metal electrodes, and are formed by depositing platinum by an electron beam evaporation method and then patterning by a lift-off method. Each scan electrode 12a and sustain electrode 12b may be formed by a pair of a transparent electrode such as ITO and a metal electrode.

Next, the scan electrode 12a and the sustain electrode 1
The dielectric glass layer is formed by printing by a known printing method such as a screen printing method and then baking so as to cover 2b.

Next, a MgO film is formed on the surface of the dielectric glass layer 13. Specifically, it is formed by depositing a MgO thin film on the surface of the dielectric glass layer 13 by an electron beam evaporation method.

Preparation of back panel PA2: back panel PA
2 has an address electrode 17 formed on a rear glass substrate 16 and is covered with an electrode protection layer 18 to form an electrode protection layer 1.
The barrier ribs 19 are formed on the surface of No. 8 and then the phosphor layer 20 is formed, whereby the phosphor layer 20 is manufactured.

The address electrodes 17 are the rear glass substrate 16
The scan electrode 12a and the sustain electrode 12b are formed on the upper surface by the same method.

The electrode protective layer 18 is formed by printing on the address electrodes 17 by using a printing method such as a screen printing method, and then firing it. The electrode protective layer 18 is made of the same glass as the dielectric glass layer 13. Titanium oxide (T
iO ₂ ) A thin film containing particles.

The partition wall 19 is formed by applying a partition wall forming material by a method such as a screen printing method, a lift-off method, or a sandblasting method, firing this, and then subjecting the partition wall top to a processing treatment. .

The phosphor layer 20 is formed by a method such as a screen printing method or a nozzle spraying method.

Panel pasting: Next, front panel PA
1 and the rear panel PA2 as the scan electrode 12a and the sustain electrode 1
2b and the address electrode 17 are aligned so as to be orthogonal to each other, and both panels are bonded together. Then, a discharge gas (for example, He-Xe) is discharged into the discharge space 30 partitioned by the partition wall 19.
System, a Ne-Xe system inert gas) is filled at a predetermined pressure.

[0127]

As described above, according to the present invention, a plurality of electrode pairs of a first electrode and a second electrode arranged in stripes are arranged in parallel, and the plurality of electrode pairs are made of a dielectric material. A plasma display panel in which a first substrate covered with a layer and a second substrate having a third electrode arranged in stripes are arranged to face each other with a partition interposed. , The dielectric layer is represented by AlNX, and the X is Si, G
It is characterized by being at least one selected from e, Sn, Pb, Be, Mg, Ca, O, and S. In addition, the dielectric layer is Mg
It is represented by OX, and the X is at least one selected from Al, Ga, Li, F, Cl, N, and P. Thereby, in the surface layer of the dielectric layer, it is possible to obtain a protective layer having high electron emission capability, excellent sputter resistance, and less affected by the impurity gas. As a result, it is possible to improve the responsiveness of discharge occurrence to voltage application, display a good image, and prolong the product life.

[Brief description of drawings]

FIG. 1 is a partial perspective view showing a conventional plasma display panel.

FIG. 2 is a block diagram showing a connection state between a plasma display panel and a drive circuit, which is common to the related art and the invention.

FIG. 3 is a time chart showing driving waveforms of a plasma display panel common to the conventional art and the present invention.

[Explanation of symbols]

PA1 Front panel PA2 Rear panel 1 AC surface discharge type plasma display panel (PD
P) 11 Front glass substrate 11a Surface 12a Scan electrode 12b Sustain electrode 12c Discharge gap 13 Dielectric glass layer 14 Protective layer 16 Rear glass substrate 17 Address electrode 18 Electrode protective layer 19 Partition 20 Phosphor layer 30 Discharge space 220 Address drive unit 230 Scan electrode driver 240 Sustain electrode driver

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hideaki Adachi             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. (72) Inventor Masahiro Deguchi             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. (72) Inventor Kazuyuki Hasegawa             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. (72) Inventor Koichi Kodera             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. (72) Inventor Hidetaka Higashino             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. (72) Inventor Uenoyama             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. F-term (reference) 5C015 HH02                 5C040 FA01 GB03 GB14 GC02 GC18                       GD07                 5C058 AA11 AB01 BA26 BA35

Claims (25)

[Claims] 1. A composition formula represented by AlNX, wherein X is Si or G.
A discharge electrode material that is at least one selected from e, Sn, Pb, Be, Mg, Ca, O, and S. 2. The composition formula (Al _1-ab M _a D _b ) (N _1-c A _c ) (M
Is at least one selected from Si, Ge, Sn, and Pb. D
Is at least one selected from Be, Mg, and Ca. A is O, S
At least one selected from. 0 ≦ a ≦ 0.5, 0 ≦ b ≦ 0.5,
0 ≦ a + b ≦ 0.5, 0 ≦ c ≦ 0.5, 0 <a + b + c ≦ 1. ) Discharge electrode material represented by. 3. At least one element selected from element M (M is an element selected from Si, Ge, Sn, and Pb) or element A (A is an element selected from O and S) , N-type doped electrode material. 4. A P-type discharge electrode material containing at least one element selected from the elements D (D is an element selected from Be, Mg and Ca). 5. At least one element selected from element M (M is an element selected from Si, Ge, Sn and Pb) or element A (A is an element selected from O and S), and an element D (D is Be, M
A discharge electrode material containing at least one element selected from g and elements selected from Ca at the same time. 6. A discharge electrode material having at least AlN as a mother structure, wherein at least a part of the atomic position of Al is Si, G
A discharge electrode material substituted with at least one element selected from e, Sn, Pb, Be, Mg, and Ca. 7. A discharge electrode material having at least AlN as a mother structure, wherein at least a part of the element N is replaced with at least one element selected from O or S. 8. The composition formula _{(Al 1-ab M a D} b) 1- δ (N 1-c A c)
δ (M is at least 1 selected from Si, Ge, Sn, Pb
seed. D is at least one selected from Be, Mg and Ca. A is
At least one selected from O and S. 0.3 <δ <0.5. ) Discharge electrode material represented by. 9. A substrate formed on a substrate and having at least (00
2) The surface is preferentially oriented to the plane.
8. The discharge electrode material according to any one of 8. 10. The composition formula is represented by MgOX, wherein X is Al, G
A discharge electrode material that is at least one selected from a, Li, F, Cl, N, and P. 11. A composition formula (Mg _1-ab M _a D _b ) (O _1-cd A _c Z
_d ) (M is at least one selected from Al, Ga, Si, Ge and Sn. D is Li and A is at least one selected from F and Cl.
Z is at least one selected from N and P. 0 ≦ a ≦ 0.5, 0 ≦
b ≦ 0.5, 0 ≦ a + b ≦ 0.5, 0 ≦ c ≦ 0.5, 0 ≦ d ≦ 0.5, 0 <a + b
Discharge electrode material represented by + c + d ≦ 1). 12. At least one element selected from element M (M is an element selected from Al, Ga, Si, Ge and Sn) or element A (A is an element selected from F and Cl). And an n-type doped electrode material. 13. Element D (D is Li) or Z (Z is N, P)
A discharge electrode material comprising at least one element selected from the group (1) selected from the above, and being p-type doped. 14. At least one element selected from the element M (M is an element selected from Al, Ga, Si, Ge and Sn) or the element A (A is an element selected from F and Cl). And the element D (D
Is at least one element selected from Li) or Z (Z is an element selected from N and P) at the same time. 15. A discharge electrode material having at least MgO as a mother structure, wherein at least a part of the atomic positions of Mg is Al,
A discharge electrode material substituted with at least one element selected from Ga and Li. 16. A discharge electrode material having a matrix structure of at least MgO, wherein at least part of the element O is F, Cl, N, P.
A discharge electrode material substituted with at least one element selected from 17. The composition formula _{(Mg 1-ab M a D} b) 1- δ (O 1-cd
A _c Z _d ) δ (M is at least one selected from Al, Ga, Si, Ge and Sn. D is at least one selected from Li, A is at least F and Cl. Z is selected from N and P. At least one selected, 0.3 <δ
<0.5. ) Range of discharge electrode material. 18. The discharge electrode material according to claim 10, wherein the discharge electrode material is formed on a substrate and has a (111), (200) or (220) plane preferential orientation. 19. The discharge electrode material according to claim 1, which is formed on a substrate and has a composition modulation structure in a direction perpendicular to the substrate surface. 20. The discharge electrode material according to claim 1, which is formed on a substrate and has a columnar structure. 21. The width of a crystal having a columnar structure is 50 nm to 30.
It is 00 nm, The discharge electrode material in any one of Claims 1-20. 22. When the inclination of the columnar structure with respect to the substrate surface is α, the range is 30 ° <α <90 °.
21. The discharge electrode material according to any one of 21. 23. Formed on a substrate, at least 0.1.
The discharge electrode material according to any one of claims 1 to 22, which has a lattice strain of not less than 2% and not more than 2%. 24. A first substrate in which a plurality of electrode pairs of a first electrode and a second electrode arranged in a stripe pattern are arranged in parallel, and the plurality of electrode pairs are covered with a dielectric layer. And the third
2. A plasma display panel in which the second substrate on which the electrodes are arranged in a stripe pattern are arranged to face each other with a partition wall interposed therebetween, and the dielectric layer is formed.
23. A plasma display panel characterized by being coated with the discharge electrode material according to any one of 23. 25. A plasma display, wherein the film thickness of the discharge electrode material according to claim 1 is 0.05 nm or more and 1000 nm or less.